Olefin extraction



Oct. 12, 1948.

c. o. roNGBERG OLEFIN EXTRACTION Filed NOV. 24, 1945 dvprm. OFJ

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duz/OP hun 70.uud .l ,rzmfJOmw Carl rzqberq 3m/enter Qbbornu Patented Oct. 12, 1948 oLaFm nxmc'non l Carl 0. Tongberg, Westfield, N. J., alu-signor to Y Standard Oll Development Company, a corporation of Delaware Application November 24, 1945'. serial No. 630,619

(ci. eso-asis) l 7 Claims. This Vinvention relates to in-:lprovements4 in the 'separation and recovery -of mono-.olens and diolens separated by means of solvents from hydrocarbon mixtures containing mono-oleflns 'and' diolens.

alone various disadvantages have arisen, such as the formation of sulfones with the sulfurdioxide,

y and the-limited range of solvent power of the 'pounds which may be generally classified asv having parailinic, aromatic, naphthenic and unsaturated structures which vary over wide ranges in molecular weight. It is also known to segregate these compounds into relatively more parailinic, more aromatic. and more unsaturated fractions by means of various selective solvents or solvent mixtures. The separation of the more viscous oils is usually accomplished by means of an organic solvent selected from the class of solvents which have a preferential selectivity for the relatively less paraillnic type compounds. The solvents used ar'e generally phenol, furfural, cresols, nitrobenzene, aniline, beta beta/ dichorodiethyl ether, and the like. In these solvents or solvent mixtures the parafiinic type Ahydrocar-` raillnate. This is usually accomplished by distillation processes, providing a sufficient differential exists between the boiling points of the solvent and the oil. Other means are also employed, as, for example, re-extraction with a secondary solvent, as by washing with water and the like.

These organic solvents and extraction processes, while entirely satisfactory for securing a separation between the more relatively aromatic fractions and the relatively more parafllnic fractions, are not completely desirable for the separa- 'tion of the particular constituents from mixtures containing constituents of a similar chemical structure, that is, the separation of-the dioleilns frrm mono-oleflns.

Various inorganicand mineral acids, in conjunction with their salts of copper and silver,

.have been used for the separation of the Vdioleilns and mono-oleflns. Other solvents that have been used are liqueiled normally gaseous inorganic solvents of the character of sulfur dioxide and liquid anhydrous ammonia. Where liquefied ammonia and sulfur dioxide have been used ammonia. Improvedrresults were obtained using liquid ammonia with a substance characterized by having the ability to .increase the solvent power of the ammonia within definite critical limits, or a substance having the ability to-decrease the solvent power ofthe ammonia .within dennite critical limits. l

I he segregation of substantially pure diolefins from a mixture of diolens, mono-oleilns and paraflins is generally best accomplished by the use of two extraction zones, namely', a stripping zone to remove the dioletlns preferentially from the feed mixture of dioleilns, mono-olens and paraillns, and an enriching zone to separate and purify the dioletlns thus removed in an.extract from the other components which are, of necessity, dissolved at the same time, but to a minor degree, in the extract. In order to obtain a high recovery of .dioleflns it is necessary to extract them froml the feed hydrocarbons. In view of the widely different solubility of mono-oleiins, parafilns and dioletlns in the ammonia solvents, it is frequently desirable to use different concentrations or different modifyingusolvents in the two zones of extraction. For example, ammonia and a relatively saturated. hydrocarbon oil (paraillnic oil) or ammonia, water, and a relatively saturated oil in which the concentration of the modifying solvents. water and the oil is different in the two zones may be used as the solvents. In other instances it is desirable to employ in i the stripping section ammonia. together with solvents to increase the dissolving power, such as methylamine, in order to be able to remove completely the dioleilns from the feed. In this case a solvent to reduce the dissolving capacity of the ammonia solventis usually used at one or more points in the enriching section in order .to purify the dioleiins.

The solubility of the individual cmponents in a given ammonia solvent is dependent not only upon the type 0f thecomponent; but also upon its molecular weight. For a given type the lower molecular weight compounds are in general more soluble. For example, it has -been found that butadiene is soluble in ammonia solvent at l". to the extent of eleven per cent. Isoprene dissolved in this same solvent at the same temperature to the extent of only six per cent. Propylene was soluble to the extent of five per cent; whereas less than one per cent of the amyleneswere dissolved.

These properties of the ammonia solvents broaden their use in some instances, but restrict them in others. For example, these solvents may be used to prepare butadiene as a substantially pure extract, while any polymerization products would be rejected in the raffinate. On the other hand, the feed oil must not be too broad in molecular weight, as otherwise the lighter monooleiins would have the same solubility as the heavier dioieflns and would contaminate the extract. In extracting a cut containing from three to six carbon atom hydrocarbons, some propylene would be dissolved along with the six carbon atom diolefins; hence, pure diolens would not be obtained. In general, it is preferred that the mouid ammonia with a methyl amine modifier is ob' tained. According to this invention the diolefins or mono-olefins, are removed from the solvent ammonia by countercurrent extraction with a paraillnic oil of high boiling range and preferably one having a Saybolt viscosity ranging from about 50 to 150 seconds at 100 F.

It is much more economical to separate the mono-oleiins from the solvent ammonia by such an extraction process than it is to separate the components by distillation, the principal saving being in heat that would be required to vaporize the ammonia. i

'I'he recovery of the C4 hydrocarbons from the paraflinic oil is partially accomplished by heat stripping with closed steam or electric heat. However, a small amount of the C4 hydrocarbons will remain behind in the parafiinic oil. This may be removed by the use of live steam but the use of live steam has the disadvantage that small -amounts of water remain in the paralnic oil which may get in the anhydrous ammonia stream andalter its solvent characteristics, and in low temperature extractions, freeze up the lines. To prevent ,such occurrences, according to this invention, the parainic oil is stripped with a low boiling inert material, such as'pentane or hexane,

in place of the live steam. The small amount of the hydrocarbon, pentane or hexane, which remains dissolved in the paraiiin cil would not be serious and can be recirculated with the parafiin oil. Where Cs or higher hydrocarbons are extracted a somewhat higher boiling parailin can be used as the stripper.

The invention will be more clearly understood upon readingthe following description with reference to the accompanying drawing:

, An extract of C4 hydrocarbons obtained by treating a mixture of hydrocarbons having four carbon atoms to the molecule, and containing mono-olens and diolelns, with ammonia and a modifier, methyiamine, is passed by means of pipe I into the solvent recovery tower 2 where the temperature is raised suiiiciently high to expel ammonia by means of pipe 3. A paraihnic oil is introduced into theupper part of the tower 2. by means of pipe 4 and passed in countercurrent now to the ammonia whereby the ammonia is freed of the C4 hydrocarbons. The modifier, in this oasi? 4 methylamine, is separated with the ammonia. The parafllnic oil, substantially free of ammonia and containing the extracted C4 hydrocarbons. is then passed from tower 2 by means of pipe l to stripping tower 6, which is heated by means of closed steam coil 1, and the major portion oi the C4 hydrocarbons liberated by the heat is passed, by means of pipe 8, to storage, 4and a fraction may be recycled through pipe I5 ton pipe '5 as a reux.` The parainic oil, from which most of the C4 hydrocarbons have been removed, is then passed through pipe 9 to the middle of stripping tower I0 into which is introduced a saturated hydrocarbon boiling between 96 to 160 F., in this case pentane or hexane, by means of pipe II, the pentane or hexane being maintained in the upper part of the tower I0 while C4 hydrocarbons are Ipassed from the stripping tower by means of pipe l2, the paralnic oil, free of C4 hydrocarbons, being removed to storage tank I3 by means of pipe I4 from which the parainic oil may be recycled to the solvent recovery tower 2. The pentane or hexane is retained in the tower I0 though a'part may pass out with the parailinic oil and be recirculated, and more of the pentane or hexane is added to maintain a definite volume. When higher boiling hydrocarbons are extracted higher boil.-

ing solvents are used.

The parailinic oil used, according to this 'invention, may have a specic gravity of about 0.82 to 0.86 and a Saybolt viscosity of to 100 seconds at 100 F. but is preferably one having a specific gravityat F. of about .845 to .855, with a. Saybolt viscosity at 100 F. of 80 to 90 seconds, and a Pensky hash of 350 F. It is not intended .to limit this invention to these particular physical characteristics as a lighter or heavier parafiinic oil may be used, preferably one with an initial boiling point of at least 450 F.

What is claimed is:

1. In the extraction and segregation oi an oieiin having 4 to 5 carbon atoms to the molecule, from a mixture of hydrocarbons having a molecular weight not over 98 and containing an oleiln where ammonia. and a modier that increases the.

solvent power of the ammonia is used as a solvent pounds are not over 30, and containing a dioleiln having 4 to 5 carbon atoms to the molecule, where y to obtain an extract of the oleiln in the ammonia, the following steps which comprise passing the ammonia extract containing the olefin having from 4 to 5 carbon atoms to the molecule, in countercurrent 'ow to a. paraiiinic oil of high boiling range, and a Saybolt viscosity of at least 50 free of the olefin.

2. In the extraction and segregation of a diolen having from 4 to 5 carbon atoms to the moleeule, from a. mixture of hydrocarbons whose e molecular weight differences between the highest and lowest molecular weight hydrocarbon comammonia and a modifier, methyl amine, that increases the solvent power of the ammonia is used as a solvent to obtain an extract of the diolefin in the ammonia, the following steps which comprise passing the ammonia extract vcontaining the di- Qleiiri in countercurrent now to a paramnie ou 'the paraffinic oil from the ammonia and modifier,

heating the parafnic oil to expel the major fraction of the diolefin, having 4 to 5 carbon atoms to the molecule, and separately stripping the residual paraflinic oil with a saturated hydrocarbon boiling at a higher temperature than the said diolefin and not over 160 F. to obtain overhead a diolefin having 4 to 5 carbon atoms to the molecule, and a residue paraflinic oil substantially free of the olefin.

3. In the extraction and segregation of an olefin from a mixture of hydrocarbons having a molecular Weight difference of not over 30 between the highest and lowest molecular weight componentsv thereof and containing olefin where ammonia and a modiler that increases the solvent power of the ammonia is used as a solvent to obtain an extract of the olen in the ammonia, the following steps which comprise passing the ammonia extract containing the olefin in countercurrent flow to a parafi'inic oil having an initial boiling point of at least 450 F. and a Saybolt viscosity at 100 F. of 80 to 90 seconds, separating the Lparafnic oil from the ammonia and modifier, heating the paraffinic oil to expel the major fraction of the olefin, and separately stripping the residual parafnic oil with a saturated hydrocarbon boiling at a higher temperature than the olefin, and within a range of 96 F. to 160 F. to obtain overhead an olefin and, as a residue, paranic oil substantially free of the olen.

4. In the extraction and segregation of olefin from a mixture of hydrocarbons having molecular weight differences within a range of 15 to 30 betweenv the highest and lowest molecular weight components thereof, containing an olefin, where ammonia and methyl amine is used as a solvent to obtain an extract of the olfen in the ammonia, the following steps which comprise passing the ammonia extract containing the olen in countercurrent flow to a parafflnic oil having an initial boiling point of at least 450 F. and a Saybolt viscosity at 100 F. of 80 to 90 seconds, separating the parafinic oil substantially free of the ammonia and methyl amine, heating the paraflinic oil to expel the major fraction of the olefin and separately stripping the residual parainlc oil with a saturated hydrocarbon boiling at a higher temperature than the said olefin, and within a range of 96'- F. to 160 F. to obtain overhead an olen and.

as a residue, parafllnic oil substantially free of the olefin.

5. In the extraction and segregation of a diolen from a mixture of hydrocarbons having I molecular differences Within the range of 15 to between the highest and lowest molecular Weight components thereof and containing a diolefin, where ammonia and methyl amine is used as a solvent to obtain an extract of the diolefin in the ammonia, the following steps which comprise passing the ammonia extract containing the diolen in countercurrent flow to a par'afnic oil having an initial boiling point of at least 450 F. and a Saybolt viscosity ait 100 F. of 80 to 90 seconds, separating the parafnic oil substantially free of the ammonia and methyl amine, heating the parafllnic oil to expel the major fraction of the diolefin, and separately stripping the residual parafiinic oil with a saturated hydrocarbon boiling at a higher temperature than the olefin, and within a range of 96 F. to 160 F. to obtain overhead a diolefin and, as a residue, parafllnic oil substantially free of the diolen.

6. In the extraction and segregation of a diolefin from a mixture of hydrocarbons containing a diolen, according to claim 5, the saturated hydrocarbon used in stripping the paramnic oil is pentane.

7. In the extraction and segregation of a diolefn from a mixture of hydrocarbons containing a diolen, according to claim 5, the hydrocarbon used in stripping the parafllnic oil is hexane.

CARL O. TONGBERG.

REFERENCES CITED The following references are of' record in the file of this patent:

UNITED STATES PATENTS 

